Electroplating aqueous solution and method of making and using same

ABSTRACT

In one embodiment of the invention, an electroplating aqueous solution is disclosed. The electroplating aqueous solution includes at least two acids, copper, at least one accelerator agent, and at least two suppressor agents. The at least one accelerator agent provides an acceleration strength of at least about 2.0 and the at least two suppressor agents, collectively, provide a suppression strength of at least about 5.0. Methods of making and using such an electroplating aqueous solution are also disclosed.

TECHNICAL FIELD

Embodiments of the invention relate to an electroplating aqueoussolution for electroplating copper, a method of making such anelectroplating aqueous solution, and a method of electroplating copperonto a substrate.

BACKGROUND

Copper-based materials have currently supplanted aluminum-basedmaterials as the material of choice for interconnects in integratedcircuits (“ICs”). Copper offers a lower electrical resistivity and ahigher electromigration resistance than that of aluminum, which hashistorically been the dominant material used for interconnects.

Interconnects in an IC are becoming one of the dominant factors fordetermining system performance and power dissipation. For example, thetotal length of interconnects in many currently available ICs can betwenty miles or more. At such lengths, interconnectresistance-capacitance (“RC”) time delay can exceed a clock cycle andseverely impact device performance. Additionally, the interconnect RCtime delay also increases as the size of interconnects continues torelentlessly decrease with corresponding decreases in transistor size.Using a lower resistivity material, such as copper, decreases theinterconnect RC time delay, which increases the speed of ICs that employinterconnects formed from copper-based materials. Copper also has athermal conductivity that is about two times aluminum's thermalconductivity and an electromigration resistance that is about ten toabout one-hundred times greater than that of aluminum.

Copper-based interconnects have also found utility in other applicationsbesides ICs. For example, solar cells, flat-panel displays, and manyother types of electronic devices can benefit from using copper-basedinterconnects for the same or similar reasons as ICs.

Due to difficulties uniformly depositing and void-free filling trenchesand other small features with copper using physical vapor deposition(“PVD”) and chemical vapor deposition (“CVD”), copper interconnects aretypically fabricated using a Damascene process. In the Damasceneprocess, a trench is formed in, for example, an interlevel dielectriclayer, such as a carbon-doped oxide. The dielectric layer is coveredwith a barrier layer formed from, for example, tantalum or titaniumnitride to prevent copper from diffusing into the silicon substrate anddegrading transistor performance. A seed layer is formed on the barrierlayer to promote uniform deposition of copper within the trench. Thesubstrate is immersed in an electroplating aqueous solution thatincludes copper. The substrate functions as a cathode of anelectrochemical cell in which the electroplating aqueous solutionfunctions as an electrolyte, and the copper from the electroplatingaqueous solution is electroplated in the trench responsive to a voltageapplied between the substrate and an anode. Then, copper deposited onregions of the substrate outside of the trench is removed usingchemical-mechanical polishing (“CMP”).

Regardless of the particular electronic device in which copper is usedas a conductive structure, it is important that an electroplatingprocess for copper be sufficiently fast to enable processing a largenumber of substrates and have an acceptable yield. Additionally, thecost of the electroplating aqueous solution is also another factorimpacting overall fabrication cost of electronic devices using copper.This is particularly important in the fabrication of solar cells, whichhave to cost-effectively compete with other, potentially morecost-effective, energy generation technologies. Thus, it is desirablethat copper electroplating aqueous solutions be capable of depositingcopper in a uniform manner (i.e., high throwing power) and at ahigh-deposition rate.

A number of electroplating aqueous solutions are currently available forelectroplating copper. For example, sulfate-based electroplating aqueoussolutions are commonly used for electroplating copper. Some alkalinecopper electroplating aqueous solutions have a high-throwing power, butare not capable of rapidly depositing copper without compromising thedeposited film quality. At high-deposition rates, the copper may grow asdendrites as opposed to a more uniformly deposited film. Additionally,alkali elements (e.g., sodium and potassium) in such alkaline copperelectroplating aqueous solutions can diffuse into silicon substrates andare deep-level impurities in silicon that can compromise transistorperformance. Fluoroborate electroplating aqueous solutions can be usedfor high-speed deposition of copper. However, fluoroborateelectroplating aqueous solutions can be more expensive than, moretraditional, sulfate-based solutions. Moreover, fluoroborateelectroplating aqueous solutions may be more hazardous and difficult todispose of than many other electroplating aqueous solutions forelectroplating copper.

Therefore, there is still a need for an electroplating aqueous solutionfor electroplating copper that can deposit a high-quality film of copperat a high-speed.

SUMMARY

In one embodiment of the invention, an electroplating aqueous solutionis disclosed. The electroplating aqueous solution includes at least twoacids, copper, at least one accelerator agent, and at least twosuppressor agents. The at least one accelerator agent provides anacceleration strength of at least about 2.0 and the at least twosuppressor agents, collectively, provide a suppression strength of atleast about 5.0.

In another embodiment of the invention, a method of electroplating isdisclosed. A substrate is immersed in an electroplating aqueoussolution. The electroplating aqueous solution includes at least twoacids, copper, at least one accelerator agent, and at least twosuppressor agents. The at least one accelerator agent provides anacceleration strength of at least about 2.0 and the at least twosuppressor agents, collectively, provide a suppression strength of atleast about 5.0. At least a portion of the copper from theelectroplating aqueous solution is electroplated onto the substrate.

In yet another embodiment of the invention, a method of making anelectroplating aqueous solution is disclosed. An electroplating aqueoussolution maintained at a first temperature may be provided. Theelectroplating aqueous solution includes at least two acids and copperpresent in a concentration below a copper solubility limit, at the firsttemperature, of the at least two acids. The electroplating aqueoussolution is heated to a second temperature that is greater than thefirst temperature. Additional copper from a copper source is introducedinto the electroplating aqueous solution when the electroplating aqueoussolution is at the second temperature so that the electroplating aqueoussolution exhibits a copper concentration of at least about 50 grams perliter.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings illustrate various embodiments of the invention, whereinlike reference numerals refer to like elements or features in differentviews or embodiments shown in the drawings.

FIGS. 1A and 1B are schematic cross-sectional views of an electroplatingsystem that may be used for practicing embodiments for electroplatingcopper onto a substrate according to various methods of the invention.

FIG. 2 is graph illustrating an example of a forward-pulse currentdensity waveform that may be used to electroplate copper from any of thedisclosed electroplating aqueous solutions.

FIG. 3 is graph illustrating an example of a reverse-pulse currentdensity waveform that may be used to electroplate copper from any of thedisclosed electroplating aqueous solutions.

DETAILED DESCRIPTION

Embodiments of the invention are directed to electroplating aqueoussolutions for electroplating copper, methods of making suchelectroplating aqueous solutions, and methods of electroplating copperonto a substrate using such electroplating aqueous solutions. Thedisclosed electroplating aqueous solutions may be used forelectroplating copper onto a substrate as a film that issubstantially-free of dendrites and at a high-deposition rate (e.g.,about 10 μm per minute or more) for forming electrical interconnectsused in ICs, solar cells, and many other applications.

According to various embodiments of the invention, an electroplatingaqueous solution includes at least two acids, copper in the form ofcupric ions (Cu²⁺), at least one accelerator agent that provides anacceleration strength of at least about 2.0, and at least two suppressoragents that collectively provide a suppression strength of at leastabout 5.0. The at least two acids and the copper collectively form anelectrolyte. The at least two acids may be selected from two or more ofthe following acids: sulfuric acid, hydrochloric acid, hydroiodic acid,hydroboric acid, fluoroboric acid, and any other suitable acid. In amore specific embodiment of the invention, the at least two acidsincludes sulfuric acid present in a concentration from about 5 grams perliter (“g/L”) to about 20 g/L and hydrochloric acid present in aconcentration from about 20 mg/L to about 100 mg/L. In addition to theaforementioned at least two acids, in certain embodiments of theinvention, the electroplating aqueous solution may further include asupplemental acid selected to increase the solubility of the copper inthe at least two acids of the electroplating aqueous solution. Forexample, the supplemental acid may be selected from alkane sulfonicacid, methane sulfonic acid, ethane sulfonic acid, propane sulfonicacid, buthane sulfonic acid, penthane sulfonic acid, hexane sulfonicacid, decane sulfonic acid, dedecane sulfonic acid, fluoroboric acid,mixtures of any of the preceding supplemental acids, or another suitableacid selected to increase the solubility of the copper in the at leasttwo acids of the electroplating aqueous solution.

The copper may be present in the electroplating aqueous solution in aconcentration of at least about 50 g/L and, more particularly, fromabout 50 g/L to about 100 g/L. In a more specific embodiment of theinvention, the concentration of the copper may be at least about 85 g/Lto about 100 g/L.

As discussed above, the electroplating aqueous solution includesadditives, such as suppressor and accelerator agents that improvecertain electroplating characteristics of the electroplating aqueoussolution. As used throughout this disclosure and claims, the phrase“virgin make solution” (“VMS”) refers to an electroplating aqueoussolution without any suppressor agents and accelerator agents. For theelectroplating aqueous solution embodiments described herein, the VMSincludes the at least two acids and the copper dissolved therein. Asused throughout this disclosure and claims, “suppression strength” ofone or more suppressor agents of an electroplating aqueous solution isdetermined by a decrease in current density at a cathode of anelectrochemical cell that includes a suppressed solution containing VMSand the one or more suppressor agents compared to current density at acathode of an electrochemical cell that includes a solution containinggenerally only the VMS, with each current density measured at about −0.7volts relative to a mercurous sulfate electrode (“MSE”). For theelectroplating aqueous solution embodiments described herein, asuppressed solution includes the at least two acids, the copper, and theat least two suppressor agents. As merely an example, when a currentdensity at a cathode of an electrochemical cell utilizing a suppressedsolution is five times lower than a current density of anelectrochemical cell utilizing a VMS, a suppressor agent provides asuppression strength of 5.0.

As used throughout this disclosure and claims, “acceleration strength”of one or more accelerator agents of an electroplating aqueous solutionis measured by an increase in current density at a cathode of anelectrochemical cell that includes an accelerated solution containingVMS and the one or more accelerator agents compared to current densityat a cathode of an electrochemical cell that includes theabove-described suppressed solution, with each current density measuredat about −0.7 volts relative to a MSE. For the electroplating aqueoussolution embodiments described herein, an accelerated solution includesthe at least two acids, the copper, and the at least one acceleratoragent. As merely an example, when a current density at a cathode of anelectrochemical cell utilizing an accelerated solution is two timeshigher than a current density of an electrochemical cell utilizing asuppressed solution, an accelerator agent provides acceleration strengthof 2.0.

The at least one accelerator agent of the electroplating aqueoussolution is formulated to increase the deposition rate of copper onto asubstrate and present in the electroplating aqueous solution in anamount sufficient to provide an acceleration strength of at least about2.0. The at least one accelerator agent may further increase thebrightness of the electroplated copper film and other qualities, such asdecreasing void concentration in the electroplated copper film. The atleast bne accelerator agent may be present in the electroplating aqueoussolution in concentration from about 10 mg/L to about 1000 mg/L.According to various embodiments of the invention, the at least oneaccelerator agent may be selected from an organic sulfide compound, suchas bis(sodium-sulfopropyl)disulfide, 3-mercapto-1-propanesulfonic acidsodium salt, N,N-dimethyl-dithiocarbamyl propylsulfonic acid sodiumsalt, 3-S-isothiuronium propyl sulfonate, or mixtures of any of thepreceding chemicals. Additional suitable accelerator agents include, butare not limited to, thiourea, allylthiourea, acetylthiourea, pyridine,mixtures of any of the preceding chemicals, or another suitableaccelerator agent. The at least one accelerator may also comprise aninorganic compound selected to increase the deposition rate of thecopper from the electroplating aqueous solution, decrease hydrogenevolution that can increase the porosity in the electroplated copperfilm, or both. For example, suitable inorganic compounds may compriseselenium-containing anions (e.g., SeO₃ ²⁻ and Se²⁻),tellurium-containing anions (e.g., TeO₃ ²⁻ and Te²⁻), or both.Additionally, many of the disclosed accelerator agents may besubstantially-free of alkali elements (e.g., sodium and potassium),which can be detrimental to the performance of semiconductor devicesused in ICs. Accordingly, a copper film deposited from one of thedisclosed electroplating aqueous solutions having an accelerator agentthat is substantially free of alkali elements will also besubstantially-free of alkali elements.

The at least two suppressor agents of the electroplating aqueoussolution are formulated to substantially suppress formation of dendritesduring electroplating copper from the electroplating aqueous solutionand improve other qualities of an electroplated copper film, such assurface roughness, ductility, brightness, and electrical conductivity.The at least two suppressor agents may be, collectively, present in theelectroplating aqueous solution in concentration from about 10 mg/L toabout 1000 mg/L. Together, the at least two suppressor agents arepresent in the electroplating aqueous solution in an amount sufficientto provide a suppression strength of at least about 5.0. The suppressoragents may be a surfactant, a leveler agent, a wetting agent, achelating agent, or an additive that exhibits a combination of any ofthe foregoing functionalities. The at least two suppressor agents may beselected from two or more of the following suppressor agents: aquaternized polyamine, a polyacrylamide, a cross-linked polyamide, aphenazine azo-dye (e.g., Janus Green B), an alkoxylated aminesurfactant, a polyether surfactant, a non-ionic surfactant, a cationicsurfactant; an anionic surfactant, a block copolymer surfactant,polyacrylic acid, a polyamine, aminocarboxylic acid, hydrocarboxylicacid, citric acid, entprol, edetic acid, tartaric acid, and any othersuitable suppressor agent.

The electroplating aqueous solutions may be manufactured according to anumber of different embodiments. According to one embodiment of theinvention, a container may be provided that contains an electrolyteincluding the at least two acids and copper dissolved in the at leasttwo acids. The electrolyte is maintained at a first temperature that maybe, for example, about room temperature (e.g., about 20° C.). The coppermay be present in the electrolyte in a concentration that is at or belowa solubility limit, at the first temperature, of the copper in theelectrolyte. For example, the copper may be present in the electrolytein a concentration that is at or below 50 g/L. Next, the electrolyte isheated to a second temperature that is greater than the firsttemperature. At the second temperature, the copper has a highersolubility in the electrolyte. The second temperature may be atemperature at which a copper electroplating process may be performed,such as about 50° C. or more.

Then, additional copper from a copper source is added to the electrolytewhile the electrolyte is maintained at the second temperature. Thecopper source may be one or more of the following copper sources: acopper salt (e.g., copper sulfate), copper oxide, and copper hydroxide.The amount of the additional copper may be selected so that the copperconcentration in the electrolyte is at or approaches the coppersolubility limit, at the second temperature, for the electrolyte. Forexample, the additional copper may be added to the electrolyte toincrease the copper concentration thereof to about 50 g/L to about 100g/L. In certain embodiments of the invention, the additional copper maybe added to the electrolyte so that the copper concentration of theelectrolyte, at the second temperature, is at least about 85 g/L. The atleast one accelerator agent and the at least two suppressor agents maybe mixed with the electrolyte prior to heating the electrolyte to thesecond temperature or after adding the additional copper.

When precipitation of copper is not a concern, the electroplatingaqueous solution may be formulated merely by mixing the selected atleast two acids, copper salt, at least one accelerator agent, and the atleast two suppression agents. For example, when the fluoroboric acidcomprises one of the at least two acids, the solubility of coppertherein is sufficiently high at room temperature so that additionalcopper does not need to be added at a higher temperature to increase thecopper concentration to a desired level.

FIG. 1A is a schematic cross-sectional view of an electroplating system100 that may be used for practicing embodiments for electroplatingcopper onto a substrate according to various methods of the invention.The electroplating system 100 may include a number of linearly spacedand isolated containers. However, in other configurations, thecontainers may be radially spaced and isolated from each other. Forexample, the electroplating system 100 may include a cleaning container101 holding a cleaning solution 102, a rinse container 103 holding arinsing solution 104 (e.g., water), an electroplating container 105holding an electroplating aqueous solution 106 that may be any of thepreviously described embodiments of electroplating aqueous solutions, apost-plating cleaning container 107 holding a post-plating cleaningsolution 108, and a drying container 109 for drying a plated substrateafter cleaning in the post-plating cleaning container 107. For example,the cleaning solution 102 may include one or more suppressor agents. Inone embodiment of the invention, the one or more suppressor agents ofthe cleaning solution 102 may have the same composition of one of thesuppressor agents used in the electroplating aqueous solution 106. Thedrying container 109 may hold a drying solution 110 (e.g., isopropylalcohol (“IPA”) in water or other drying solution) to effect removal anypost-plating cleaning solution 108 on the substrate or the substrate maybe spin dried. Although not shown, external heaters may maintain thetemperature of the electroplating aqueous solution 106 disposed withinthe electroplating container 105 at a selected electroplatingtemperature, such as between about 20° C. to about 60° C.

The electroplating system 100 further includes an actuator system 111that is operably coupled to a substrate holder 112 via a movable arm114. The actuator system 111 is operable to controllably and selectivelymove the substrate holder 112 upwardly and downwardly in verticaldirections V₁ and V₂ and horizontally in horizontal directions H₁ andH₂. The substrate holder 112 is configured to hold a substrate 116having a surface 117 on which a copper film 119 is electroplated andfurther includes provisions, such as electrical contact pins, thatelectrically contact the substrate 116. It should be emphasized that anysuitable substrate holder 114 may be used. Although only a singlesubstrate is illustrated in FIG. 1A for simplicity, many commerciallyavailable substrate holders are configured to hold multiple substrates.Additionally, the term “substrate” refers to any workpiece capable ofbeing electroplated. For example, suitable substrates include, but arenot limited to, semiconductor substrates (e.g., single-crystal siliconwafers, single-crystal gallium arsenide wafer, etc.) with or withoutactive and/or passive devices (e.g., transistors, diodes, capacitors,resistors, etc.) formed therein, printed circuit boards, flexiblepolymeric substrates, and many other types of substrates. Additionally,a variety of different fluid supply systems may be employed to supplythe various fluids in the containers 101, 103, 105, 107, and 109 and,optionally, to re-circulate the electroplating aqueous solution 106 toprovide a generally laminar flow of the electroplating aqueous solution106 over the substrate 116. Such fluid supply systems and containerconfigurations are well-known and in the interest of brevity are notdescribed in detail herein. Referring to FIG. 1B, in otherconfigurations, the substrate holder 112 may be positioned so that thesurface 117 of the substrate 116 is oriented in a downward direction (asshown) or an upward direction, and the actuator system 111 is operableto rotate the substrate holder 112 and substrate 116 in a direction R.

The electroplating system 100 further includes a voltage source 118 thatis electrically connected to the substrate holder 112 (i.e., thecathode) and consequently, the substrate 116. The voltage source 118 isfurther electrically connected to an anode 120 immersed in theelectroplating aqueous solution 106 of the electroplating bath 105. Theanode 120 may be spaced a distance S from the surface 117 of thesubstrate 116. For example, the distance S may be about 0.1 centimeters(“cm”) to about 10 cm and, more specifically about 1 cm. The voltagesource 118 is operable to apply a selected voltage between the substrate116 and the anode 120.

Various embodiments of methods of the invention for electroplatingcopper onto the substrate 116 will now be discussed below in more detailin conjunction with FIGS. 1A and 1B. In practice, the actuator system111 may immerse the substrate holder 112 carrying the substrate 116 intothe cleaning solution 102, followed by immersing the substrate holder112 carrying the substrate 116 into the rinsing solution 104. Next, theactuator system 111 may immerse the substrate holder 112 carrying thesubstrate 116 into the electroplating aqueous solution 106. While thesubstrate 116 immersed in the electroplating aqueous solution 106, thevoltage source 118 may apply a voltage between the substrate 116 and theanode 120 to cause copper from the electroplating aqueous solution 106to plate onto surface 117 of the substrate 116 to form the copper film119.

While the substrate 116 is immersed in the electroplating aqueoussolution 106 and copper is being electroplated onto the surface 117 ofthe substrate 116, the actuator system 111 may move the substrate holder112 and the substrate 116 in a linear oscillatory manner in thedirections V₁ and V₂. For example, the substrate 116 may be linearlyoscillated at a rate of about 10 millimeters per second (“mm/s”) toabout 1000 mm/s and with a stroke length of about 600 mm. In oneembodiment of the invention, when the substrate 116 has a diameter ofabout 300 mm, the substrate 116 is linearly oscillated at a frequency ofabout 100 strokes/min. In some embodiments of the invention, the strokelength may be equal to or greater than dimension D of surface 117 to beelectroplated.

With reference to FIG. 1B, in another embodiment of the invention, thesubstrate holder 116 and substrate 112 may be rotated in the direction Ras a unit while the surface 117 of the substrate 116 is maintainedgenerally parallel to a longitudinal axis of the anode 120. For example,the substrate holder 116 and substrate 112 may be rotated in thedirection R as a unit at a rotational speed of about 150 revolutions perminute (“RPM”) to about 300 RPM and, more particularly, about 200 RPM.In other embodiments of the invention, a combination of linearoscillatory movement of the substrate holder 112 and substrate 116 as aunit in the directions H₁ and H₂ and rotational movement in thedirection R may be used. Utilizing any of the above-described techniquesfor linearly oscillating and/or rotating the substrate 112 enablesincreasing the limiting current density at the substrate 116 that islimited by diffusion of cupric ions within the electroplating aqueoussolution 106 to the surface 117 of the substrate 116. Consequently,increasing the current density at the substrate 116 increases theelectroplating deposition rate of the copper film 119. For example,utilizing any of the above substrate-movement techniques in combinationwith the chemistry of the electroplating aqueous solution 106 enablesthe voltage source 118 to impose a current density at the substrate 116of about 200 milliamps per square centimeter (“mA/cm²”) to about 2000mA/cm². At such high current densities, the deposition rate of copperonto the surface 117 of the substrate 116 may be 10 μm per minute ormore. Furthermore, the deposited copper film 119 may be substantiallydendrite-free despite being deposited at such a high-deposition rate.

When the anode 120 is an inert anode, copper can be continually added tothe electroplating aqueous solution 106 to maintain a generally constantconcentration of copper as the copper film 119 is deposited. When theanode 120 is a consumable copper anode, copper from the anode 120 may beoxidized and dissolved in the electroplating aqueous solution 106 tomaintain a generally constant concentration of copper as the copper film119 is deposited.

In certain embodiments of the invention, the voltage source 118 mayapply a time-varying voltage to impose a forward-pulse current densityon the substrate 116 to promote forming a finer grain size in the copperfilm 119. For example, FIG. 2 shows one example of a forward-pulsecurrent density waveform 200 that may be imposed on the substrate 116 byapplying a voltage between the substrate 116 and the anode 120 using thevoltage source 118. Representative current-densities at the substrate112 (i.e., the cathode) for the forward-pulse current density waveform200 may be about 200 mA/cm² to about 2000 mA/cm². In other embodimentsof the invention, the voltage source 118 may apply a time-varyingvoltage to impose a reverse-pulse current density waveform on thesubstrate 116 or a combination of a forward-pulse and reverse-pulsecurrent density waveform. For example, FIG. 3 shows one example of aforward-pulse/reverse-pulse current density waveform 300 in which thecurrent density at the substrate 116 may be periodically reversed.Representative current densities at the substrate 112 (i.e., thecathode) for the forward pulse of the forward-pulse/reverse-pulsecurrent density waveform 300 may be increased to about 10 A/cm² with apulse duration, t, of about 0.1 ms to about 100 ms.

After electroplating the copper film 119 onto the substrate 116, theactuator system 111 may move and immerse the substrate holder 112 andsubstrate 116 into the post-plating cleaning solution 108 of thepost-plating cleaning container 107. Then, the actuator system 111 maymove and immerse the substrate holder 112 and substrate 116 into thedrying solution 110 of the drying container 109.

The disclosed electroplating aqueous solutions may be used forelectroplating a high-quality copper film at a high-deposition rate toform many different types of electrically conductive structures. Forexample, copper electroplated according to methods disclosed herein maybe used to form interconnects for ICs using a Damascene process. Copperelectroplated according to methods disclosed herein may also be used toform through-substrate interconnects, through-mask plated films,electroplated bumps for flip-chip type electrical connections, or othermetallization structures in ICs and other electronic devices. Moreover,copper electroplated according to methods disclosed herein may also beused to form electrical contacts for solar cells. The foregoing,non-limiting, list of applications merely provides some examples of usesof copper electroplated according to methods disclosed herein.

From the foregoing it will be appreciated that, although specificembodiments of the invention have been described herein for purposes ofillustration, various modifications may be made without deviating fromthe spirit and scope of the invention.

1. An electroplating aqueous solution, comprising: at least two acids;copper; at least one accelerator agent that provides an accelerationstrength of at least about 2.0; and at least two suppressor agents thatcollectively provide a suppression strength of at least about 5.0. 2.The electroplating aqueous solution of claim 1 wherein the at least twoacids comprise one or more of the following acids: sulfuric acid;hydrochloric acid; hydroiodic acid; hydroboric acid; and fluoroboricacid.
 3. The electroplating aqueous solution of claim 1 wherein the atleast two acids comprise: sulfuric acid present in a concentration fromabout 5 grams per liter to about 20 grams per liter; and hydrochloricacid present in a concentration from about 20 milligrams per liter toabout 100 milligrams per liter.
 4. The electroplating aqueous solutionof claim 1 wherein the copper is present in a concentration from about50 grams per liter to about 100 grams per liter.
 5. The electroplatingaqueous solution of claim 1 wherein the concentration is at least about85 grams per liter.
 6. The electroplating aqueous solution of claim 1wherein the at least one accelerator agent comprises at least one of: asulfide compound; a selenium-containing anion; and atellurium-containing anion.
 7. The electroplating aqueous solution ofclaim 1 wherein the at least two suppressor agents comprise one or moreof the following suppressor agents: a surfactant; a chelating agent; aleveler agent; and a wetting agent.
 8. The electroplating aqueoussolution of claim 1 wherein the at least two suppressor agents compriseone or more of the following suppressor agents: a quaternized polyamine;a polyacrylamide; a cross-linked polyamide; a phenazine azo-dye; analkoxylated amine surfactant; a polyether surfactant; a non-ionicsurfactant; a cationic surfactant; an anionic surfactant; a blockcopolymer surfactant; polyacrylic acid; a polyamines; aminocarboxylicacid; hydrocarboxylic acid; citric acid; entprol; edetic acid; andtartaric acid.
 9. The electroplating aqueous solution of claim 1wherein: the at least one accelerator agent is present in aconcentration from about 10 milligrams per liter to about 1000milligrams per liter; and the at least two suppressor agents arecollectively present in a concentration from about 10 milligrams perliter to about 1000 milligrams per liter.
 10. The electroplating aqueoussolution of claim 1 wherein: the at least two acids are, collectively,present in a concentration from about 5 grams per liter to about 20grams per liter; and the copper is present in a concentration from about50 grams per liter to about 100 grams per liter.
 11. A method ofelectroplating, comprising: immersing a substrate in an electroplatingaqueous solution, the electroplating aqueous solution comprising: atleast two acids; copper; at least one accelerator agent that provides anacceleration strength of at least about 2.0; and at least two suppressoragents that collectively provide a suppression strength of at leastabout 5.0; and electroplating at least a portion of the copper from theelectroplating aqueous solution onto the substrate.
 12. The method ofclaim 11, further comprising linearly oscillating the substrate in theelectroplating aqueous solution during the act of electroplating. 13.The method of claim 12 wherein linearly oscillating the substrate in theelectroplating aqueous solution comprises: linearly oscillating thesubstrate in the bath at a rate of about 10 millimeters per second toabout 1000 millimeters per second.
 14. The method of claim 11, furthercomprising rotating the substrate in the electroplating aqueous solutionduring the act of electroplating.
 15. The method of claim 14 whereinrotating the substrate in the electroplating aqueous solution comprises:rotating the substrate in the electroplating aqueous solution at a rateof about 150 revolutions per minute to about 300 revolutions per minute.16. The method of claim 14: wherein the substrate comprises a surface tobe electroplated with the copper; and further comprising orienting thesurface in an upwardly facing direction or downwardly facing direction.17. The method of claim 14: wherein the substrate comprises a surface tobe electroplated with the copper; further comprising moving thesubstrate in a manner that maintains the surface substantially parallelto a longitudinal axis of an anode immersed in the electroplatingaqueous solution.
 18. The method of claim 11 wherein electroplating atleast a portion of the copper from the electroplating aqueous solutiononto the substrate comprises: depositing the copper on the substrate asa substantially dendrite-free film at a deposition rate of at least 10micrometers per minute.
 19. The method of claim 11, further comprisingadding additional copper to the electroplating aqueous solution providedfrom a consumable anode immersed in the electroplating aqueous solution.20. The method of claim 11, further comprising replenishing theelectroplating aqueous solution with additional copper introduced intothe electroplating aqueous solution.
 21. The method of claim 11, furthercomprising: prior to immersing the substrate in the electroplatingaqueous solution, cleaning the substrate in a cleaning solution thatincludes at least one suppressor agent having the same composition asone of the at least two suppressor agents of the electroplating aqueoussolution.
 22. The method of claim 11, further comprising maintaining theelectroplating aqueous solution at a temperature between about 20°Celsius to about 60° Celsius.
 23. The method of claim 11: wherein thesubstrate comprises a surface to be electroplated with the copper; andfurther comprising spacing the surface a distance of about 0.1centimeter to about 10 centimeter from an anode immersed in theelectroplating aqueous solution.
 24. The method of claim 11 wherein theat least two acids of the electroplating aqueous solution comprise oneor more of the following acids: sulfuric acid; hydrochloric acid;hydroiodic acid; hydroboric acid; and fluoroboric acid.
 25. The methodof claim 11 wherein the at least two acids of the electroplating aqueoussolution comprise: sulfuric acid present in a concentration from about 5grams per liter to about 20 grams per liter; and hydrochloric acidpresent in a concentration from about 20 milligrams per liter to about100 milligrams per liter.
 26. The method of claim 11 wherein the copperof the electroplating aqueous solution is present in a concentrationfrom about 50 grams per-liter to about 100 grams per liter.
 27. Themethod of claim 11 wherein the at least one accelerator agent of theelectroplating aqueous solution comprises at least one of: a sulfidecompound; a selenium-containing anion; and a tellurium-containing anion.28. The method of claim 11 wherein the at least two suppressor agents ofthe electroplating aqueous solution comprise one or more of thefollowing suppressor agents: a surfactant; a chelating agent; a leveleragent; and a wetting agent.
 29. The method of claim 11 wherein the atleast two suppressor agents of the electroplating aqueous solutioncomprise one or more of the following suppressor agents: a quaternizedpolyamine; a polyacrylamide; a cross-linked polyamide; a phenazineazo-dye; an alkoxylated amine surfactant; a polyether surfactant; anon-ionic surfactant; a cationic surfactant; an anionic surfactant; ablock copolymer surfactant; polyacrylic acid; a polyamines;aminocarboxylic acid; hydrocarboxylic acid; citric acid; entprol; edeticacid; and tartaric acid.
 30. The method of claim 11 wherein: the atleast one accelerator agent is present in a concentration from about 10milligrams per liter to about 1000 milligrams per liter; and the atleast two suppressor agents are collectively present in a concentrationfrom about 10 milligrams per liter to about 1000 milligrams per liter.31. The method of claim 11 wherein: the at least two acids of theelectroplating aqueous solution are, collectively, present in aconcentration from about 5 grams per liter to about 20 grams per liter;and the copper of the electroplating aqueous solution is present in aconcentration from about 50 grams per liter to about 100 grams perliter.
 32. A method of making an electroplating aqueous solution,comprising: maintaining an electroplating aqueous solution at a firsttemperature, the electroplating aqueous solution including: at least twoacids; copper present in a concentration below a copper solubilitylimit, at the first temperature, of the at least two acids; heating theelectroplating aqueous solution to a second temperature that is greaterthan the first temperature; and introducing additional copper from acopper source to the electroplating aqueous solution when theelectroplating aqueous solution is at the second temperature so that theelectroplating aqueous solution exhibits a copper concentration of atleast about 50 grams per liter.
 33. The method of claim 32 whereinintroducing additional copper from a copper source comprises:introducing additional copper in a concentration that is less than acopper solubility limit of the at least two acids at the electroplatingtemperature.
 34. The method of claim 32 wherein introducing additionalcopper comprises: introducing the additional copper into theelectroplating aqueous solution in an amount so that the copperconcentration is about 50 grams per liter to about 100 grams per literat the second temperature.
 35. The method of claim 32 whereinintroducing additional copper from a copper source comprises:introducing the additional copper into the electroplating aqueoussolution in an amount so that the copper concentration is about 85 gramsper liter or more at the second temperature.
 36. The method of claim 32wherein the copper source comprises at least one of: a copper salt;copper oxide; and copper hydroxide.
 37. The method of claim 31 whereinthe electroplating aqueous solution comprises at least one acceleratoragent that provides an acceleration strength of at least about 2.0 andat least two suppressor agents that collectively provides a suppressionstrength of at least about 5.0.